CN1035496A - Use purification of acetic acid with ozone - Google Patents
Use purification of acetic acid with ozone Download PDFInfo
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- CN1035496A CN1035496A CN88108769A CN88108769A CN1035496A CN 1035496 A CN1035496 A CN 1035496A CN 88108769 A CN88108769 A CN 88108769A CN 88108769 A CN88108769 A CN 88108769A CN 1035496 A CN1035496 A CN 1035496A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/08—Acetic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
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Abstract
Through having with ozonize or catalyst-free in the presence of purify and to contain the acetate of iodide, unsaturated materials and carbonyl impurities.
Description
The pending application of submitting on December 1st, 1,986 936188 has been introduced with the compound of hydrazine or derivatives thereof and has been handled purification of acetic acid.
The present invention relates to the purifying of acetate, particularly the purification process of the acetate of making from the methyl alcohol catalyzed carbonylation.
Can use several different methods to produce acetic acid, such as comprising the oxidizing process or directly synthetic by methyl alcohol and carbon monoxide such as acetaldehyde oxidation, naphtha, butane and similar compound. One of commercial run of the most effective preparation acetic acid is the methanol carbonylation of introducing in the United States Patent (USP) 3769329. This carbonylating catalyst is by rhodium, it or be dissolved in or be scattered in the liquid reaction medium, or be attached on the inert solid and halogen-containing catalytic promoter such as iodomethane form. Can rhodium be added reaction system with any form, and the definite character of rhodium component is irrelevant in reinforced form and evaluation (if this evaluation really if possible) active catalyst complex. Equally, not harsh to the characteristic requirements of halide promoter yet. Disclose a large amount of promoter that are suitable in the document, maximum is the organic iodine class. Generally be with catalyst dissolution in liquid reaction medium, in this liquid, pass into continuously carbon monoxide again, carry out synthetic reaction.
Submitted February 8 at the common unsettled common U.S. Patent application 699525(1985 that allows that awards) and european patent application 161874(1985 open November 21) in disclosed a kind of improvement that pure carbonylation production in the presence of rhodium catalyst is had now method than pure carboxylic acid of Duoing a carbon atom.As described therein, produce acetate (HAc) by methyl alcohol (MeOH) in reaction medium, this reaction medium is made up of the rhodium of methyl acetate (MeOAc), methyl halide (especially methyl iodide MeI) and effective catalysis concentration.This invention at first is to find by keep the rhodium of effective catalytic amount in reaction medium, at least finite concentration water, methyl acetate and methyl iodide and maintenance are than the higher specific iodide ion concentration of iodide content that exists with methyl iodide or other organic iodine form, then both made in reaction medium water concentration extremely low, as 4%(weight) or lower, also can keep the productive rate of very high-caliber catalyst stability and carbonylation reaction agent under the situation of (being maintained at about 14% or 15%) although in the general industry production be.Iodide ion exists with the form of simple salt, and is good with lithium iodide.This application points out that the concentration of methyl acetate and salt compounded of iodine is to influence two important factors that carbonylation of methanol generates the speed of acetate, and is especially all the more so when the concentration of reagent water is hanged down.Use the methyl acetate and the salt compounded of iodine of higher concentration, both made in the liquid reaction medium aqueous concentration low to about 0.1%(weight) time, also can obtain the catalyst stability and the reagent productive rate of unexpected level, so low water-content broadly simple defining is the water of " limited concentration ".In addition, used reaction medium has also improved the stability of rhodium catalyst, as stop catalyst sedimentation, especially aborning all the more so during the product recovery stage, in this stage, easily remove the carbon monoxide in the catalyzer when distilling, and under the environment of carbon monoxide in reaction vessel, be the ligand that rhodium is had stabilization for the recovery acetic acid product.This paper quotes U.S. Patent application 699525 files as a reference.
Can according to a conventional method as will be purified by the acetate that carbonylation of methanol is made by a series of distillations is high purity product.Although also can produce the higher acetate of purity with this method, contain a certain amount of by-product impurities in the acetic acid product, this can measure the reducing activity of permanganate according to it.The content of these reducing impurities can be represented with permanganate time.Permanganate time is an important commerical test, and the carboxylic acid product all must satisfy the requirement of this test, because be extremely deleterious in the existence of this class impurity of many application facet.Because these impurity can steam with acetate, only adopt conventional method of purification obviously to be difficult to remove these a spot of impurity.
In the remaining impurity of being found that can reduce permanganate time, the easiest by carried secretly in the catalyst solution of reactor enter product liquid stream to calculate alkyl iodide impurities.In acetic acid product, also find multiple nonsaturation carbonyl impurities, comprise crotonaldehyde, ethyl crotonaldehyde and 2-methyl thereof-2-pentenals isomer.As previously mentioned, because the amount of iodide, unsaturated compound and carbonyl impurities is few, it is very difficult therefore to adopt physical method to remove these impurity from the acetate goods, and the cost height.Thereby the impurities removing method of a kind of economy of needs.
Proposed multiple purification carboxylic acid or removed the method for nonacid component from acid, for example: United States Patent (USP) 4576683 has disclosed a kind of C of making
1To C
10Aliphatic carboxylic acid and C
3To C
10The method that alkene class carboxylic acid is separated from the mixture with nonacid material, this method are to use acid amides to do extraction agent extractive distillation, obtain the mixture of extraction agent-acid, from then on obtain acid in extraction agent-acid mixture through rectification and purification again.It is said this method of this patent introduction be specially adapted to contain unconverted hydro carbons and oxygenated compound thereof as with alcohol, aldehyde and/or ketone, and the separation of the aqueous mixture of formic acid, acetate and/or the propionic acid of other impurity that produces as oxidizing reaction that also may contain is purified.The acid amides extraction agent of selecting for use in this patent is the lactan with 5 or 6 yuan of rings.Pyrrolidone and derivative thereof have been introduced especially.
United States Patent (USP) 4268362 provides the method that removes formaldehyde in a kind of thick acetic acid product of making from building-up reactions (as acetaldehyde oxidation, butane gas phase or liquid phase oxidation, petroleum naphtha or paraffin oxidation style and methyl alcohol and reaction of carbon monoxide method).This separation method is included in heating zone and handles acetate, shifts out the product of heating and send into distilling period under near acetate boiling point or higher temperature, carry out distillation procedure and obtain the acetic acid fraction of low boiler cut, high boiling fraction and medium boiling point, formaldehyde content wherein is 300ppm or lower.
United States Patent (USP) 3725208 relates to a kind of method that removes a small amount of aldehyde type impurities from vinylformic acid, it comprises to vinylformic acid adds the compound that is selected from sulfuric acid, hydrazine, phenylhydrazine, aniline, monoethanolamine, quadrol and glycine on a small quantity, distills this acrylic acid mixture then.Though hydrazine and vinylformic acid generate pyrrolidone through thermopositive reaction usually, and amine such as monoethanolamine and quadrol have the performance with vinylformic acid salify and generation aminocarboxylic acid, but the patentee points out, surprisingly these compounds main with vinylformic acid in contained aldehydes reaction also can from vinylformic acid, remove them.
Authorize Daicel Chemical Industries, the Japanese patent application 84-176729 of Ltd has introduced the method that a kind of acetate is purified, this method adds small amount of peracetic acid in the thick acetic acid product, heats these mixtures about 20 hours, distillation then in 50 ℃ to 120 ℃.
Japanese patent application 60-222439 has introduced the method for purification of the diacetyl oxide of being produced by ketene process, and this method is to be ketene with the acetate pyrolysis earlier, combines with acetate through absorption reaction then, produces diacetyl oxide.
United States Patent (USP) 2900413 is another patents of propose improving the lipid acid permanganate time, this patent disclosure heating steps and distilation steps.
The present invention relates to have or the non-oxidation catalysts in the presence of with ozone or contain ozone gas acetate is handled, purifying acetic acid and improve the method for permanganate time.Therefore, can handle by using, remove these small amount of impurities purifying acetic acids with the ozone of impurity reactions such as unsaturates, iodide and carbonyl compound by the acetate that methods such as methyl alcohol catalyzed carbonylation are made.Thereafter if desired, distillation or activated carbon adsorption that can be routinely, methods such as molecular sieve or ion exchange resin will be separated from acetate by the impurity that ozonize generates.
Ozone disaggregating treatment of the present invention is applicable to that purification is by the methyl alcohol acetate that carbonylation is produced in the presence of metal catalysts such as rhodium.When this carbonylation reaction be introduce in United States Patent (USP) 3769329 carry out catalysis with halogenide promotor such as metal such as rhodium and Organohalogen compounds the time, method of purification of the present invention is effective especially.When under the low condition of water-content, producing acetate with methanol carbonylation, such as in United States Patent (USP) 699525 proposition, catalyst solution wherein not only contains rhodium catalyst and Organohalogen compounds promotor, but also contain other salt compounded of iodine, then the method for purifying acetic acid of the present invention is effective especially.Have been found that organic iodine impurity and undersaturated carbonyl impurities all make the commodity value of acetic acid product reduce.
Produce in the low water content carbonylation of methanol under the situation of acetate (as U.S. Patent application 699525), catalyst system therefor comprises rhodium component and halogen promotor, but halogen bromine or iodine wherein.The rhodium component of catalyst system is generally considered to be with the coordination compound form and exists, and is the halogen component and have a part in this coordination compound at least.Except that the coordination of rhodium and halogen, think that also carbon monoxide part and rhodium can form coordination compound or complex compound.Can provide the rhodium component of catalyst system by in reaction zone, adding rhodium with forms such as rhodium metal, rhodium salt and rhodium oxide compound, organic rhodium compound, rhodium coordination compoundes.
The halogen of this catalyst system promotes that component is made of the halogen compounds that comprises Organohalogen compounds.Therefore can use halogenated alkane, the halogenated alkane of halogenated aryl hydrocarbon and replacement and the haloarene compounds of replacement.This halogenide promotor is equivalent to be existed for by the form of the halogenated alkane of the alkyl of the raw alcohol of carbonylation suitable with its alkyl, for example, in carbonylation of methanol system acetate, halogenide promotor will comprise methyl halide, is good with methyl iodide.
Used liquid reaction medium can comprise any and the catalyst system mixed solvent that mixes, and can comprise the mixture of the ester of alcohol or raw polyol and/or required carboxylic acid and/or this two compounds.Solvent that is used for the comprises low-water carbonylation method and the liquid reaction medium recommended comprise the carboxylic acid product.Therefore when carbonylation of methanol system acetate, its solvent is advisable with acetate.
Also should add water in the reaction medium, but add water concentration think the water concentration that can obtain enough speed of reaction before being significantly less than.As everyone knows, in this class rhodium catalyzed carbonylation reaction of the present invention, add water speed of reaction is played a driving role, (seeing United States Patent (USP) 3769329).Water concentration when therefore, carrying out industrial production is at least 14%(weight).Thereby unexpectedly at all be lower than 14%(weight at water-content) and be low to moderate 0.1%(weight) time can obtain to be equal to or higher than substantially use 14%(weight) speed of reaction that obtains during high concentration water's content like this.
According to the most effective carbonylation method in the present invention by in reaction medium, adding a kind of being equivalent to by by of the acid of the alcohol of carbonylation with the carbonylation reaction generation, the ester that is generated, and it is a kind of except as the additional iodide ion catalytic promoter such as methyl iodide or other organic iodide, then under low water concentration condition, also can obtain satisfied speed of response.Therefore in carbonylation of methanol system acetate, used ester is a methyl acetate, and the iodine promotor that other adds is a kind of salt compounded of iodine, is good with lithium iodide.Have been found that under low water concentration condition methyl acetate and lithium iodide only play speed promotor when their concentration separately is higher, and find that promoter action is higher when two components exist simultaneously.Also do not recognize this point in the prior art before the U.S. Patent application 699525 of common transfer discloses.Compare with prior art, think that the concentration of the lithium iodide that uses is quite high in the reaction medium of the carbonylation reaction system of recommending, in the prior art almost not in this class reaction system test use halide salts.
Can closely contact and carry out carbonylation reaction being suitable for forming carbon monoxide that the raw alcohol that makes liquid phase under the temperature and pressure condition of carbonylation product and bubbling feed rhodium-containing catalyst, halogen-containing promotion component, alkyl ester and the liquid reaction medium of additional solvability salt compounded of iodine promotor.Therefore, when raw material was methyl alcohol, halogen-containing promotion component was a methyl iodide, and alkyl ester is a methyl acetate.General think that all the concentration of iodide ion is very important in the catalyst system, and unimportant with the associating positively charged ion of iodine, and under the given condition of iodine volumetric molar concentration, cationic characteristic does not resemble the effect of iodine concentration obvious.As long as sufficiently soluble in reaction medium can use any metal iodide salt or any organic cation iodide salt that the iodide of desired concn are provided.Iodide salt can be the iodide salt of organic level Four cationic salts or inorganic cation.Iodide salt is iodine and " Handbook of Chemistry and Physics " (CRC press preferably, Cleveland, Ohio, 1975-76 the 56th edition) periodic table of elements I a family in the book and the salt that a kind of metal generated of II a family.Alkaline metal iodide is particularly effective, and is good with lithium iodide.In the most useful in the present invention low water content carbonylation reaction, the consumption of additional iodide in catalyst solution except that organic iodide promotor is 2% to 20%(weight), and with 10% to 20%(weight) be advisable, the consumption of methyl acetate is 0.5% to 30%, and with 2% to 5%(weight) be advisable, the consumption of methyl iodide is 5% to 20%, with 14% to 16%(weight) be advisable.The consumption of rhodium catalyst is 200 to 1000ppm, and is advisable with 300 to 600ppm.
Typical reaction temperatures for carbonylation will is about 150 ℃ to 250 ℃, temperature range be about 180 ℃ to 220 ℃ better.The dividing potential drop of carbon monoxide can change in relative broad range in the reactor, but is generally about 2 to 30 normal atmosphere, and is advisable with about 4 to 15 normal atmosphere.Add the dividing potential drop of by product and the vapour pressure of contained liquid, the total pressure scope is about 15 to 40 normal atmosphere in the reactor.
A kind of spendable reaction and acetate are collected system, wherein use of the present invention improving one's methods, and comprise (a) liquid-phase carbonylation reactor, (b) so-called " flasher " and (C) " methyl iodide-separated from acetic acid post ".Carbonylation reactor is an autoclave that band stirs, and wherein the content of reaction liquid remains on constant density automatically.In reactor, feed continuously new methyl alcohol, add enough water in reaction medium, keeping the water of limited concentration at least, from the recycling catalyst solution of flasher bottom with from the round-robin methyl iodide and the methyl acetate of methyl iodide-separated from acetic acid capital.Can use alternately distillation system, so that can collect thick acetic acid product and to reactor cycles enter catalyst solution, methyl iodide and methyl acetate.In the method for this recommendation, carbon monoxide feeds carbonylation reactor continuously being used for stirring under the agitator of component.Adopting this method to be certain to make gas raw material to pass through reaction liquid fully disperses.From reactor, discharge and purge gas stream, with the carbon monoxide pressure of tension that prevents the gaseous by-product accumulation and keep determining under the given total reactor pressure.The temperature of reactor is automatically control, and the feeding speed of carbon monoxide raw material should be enough to the total reactor pressure that keeps required.
The speed of product liquid discharging from carbonylation reactor should be enough to keep the material in the reactor to remain on constant level, and the midpoint of this product liquid between flasher top and bottom fed flasher.To emit as bottom liquid stream (mainly be acetate to catalyst solution in flasher; Contain rhodium and iodide salt together with small amount of acetic acid methyl esters, methyl iodide and water), and flasher top composition mainly contains acetic acid product and contain methyl iodide, methyl acetate and water.The part carbon monoxide is overflowed at the flasher top together with gaseous by-product such as methane, hydrogen and carbonic acid gas.
To take out finally and purify (as requested by the known method of present technique field those of ordinary skill, preferably distillation method is removed and anhydrated etc.) then by methyl iodide-effusive acetic acid product in separated from acetic acid column bottom (also can near bottom with the discharging of effluent form).To be recycled in the carbonylation reactor with new methyl iodide from component methyl iodide-separated from acetic acid device top, that mainly contain methyl iodide and methyl acetate, the feeding speed of fresh methyl iodide should be enough to keep the desired methyl iodide concentration of liquid reaction medium in the carbonylation reactor.Needing to feed new methyl iodide is the methyl iodide that loses in flasher and the carbonylation reactor exhaust jet stream in order to replenish.
The thick product of exsiccant acetate is pure not enough, because it contains remaining by product such as organic iodide and metal iodide, unsaturated materials and carbonyl impurities, the most outstanding is crotonaldehyde, ethyl crotonaldehyde, 2-methyl-2 pentenals etc.A small amount of these impurity can reduce the industrial applicability of acetic acid product, and therefore find by using ozonize acetate, make the required purity acetate of acquisition become possibility, and this is confirmed by permanganate test.
According to an aspect of the present invention, by producing ozone gas and making it to contact, make thick acetate be subjected to the ozone Decomposition with acetic acid product physics.According to a further aspect in the invention, the ozone that carries out acetate in the presence of the oxide catalyst of effective catalytic amount decomposes.
Ozone (O
3) be the allotropic substance of oxygen, wherein be three atoms form a molecule, rather than two common atoms.Although ozone is a kind of strong oxidizer, it is not special-purpose oxygenant, therefore can oxidation any contact with it the more material of suboxide electromotive force arranged.For this reason, when it when impurity in the above-mentioned acetate contacts, it is with for example carbon-to-carbon double bond oxidation of unsaturates, unsaturates can make the permanganate time of acetic acid product shorten obviously.But do not think that this theory of operation is to understand key of the present invention.Available data hereinafter described shows that the benefit that the ozone contact is handled is, because ozone has the ability that makes iodide, unsaturated materials and carbonyl compound inactivation, prevents that thus these impurity from exerting an influence to acetate when storing or using later on.
Can carry out ozone and decompose by produce ozone by any suitable method such as quartz lamp, silent discharge or the spark discharge that is commonly referred to as corona discharge, but to use wavelength to be advisable to obtain ozone at the radiation source irradiates air or oxygen of about 1000 dust to 2950 dusts.For suitability for industrialized production ozone, adopt and in air or oxygen, use corona discharge technology better.Uv-radiation type ozonizer generally only is used for small scale systems.Regulate the maximum weight ratio that uses ozone in the liquid acetic acid by the flammability limit value of acetate one oxygen vapor phase composition.Among the described hereinafter embodiment, the middle part of ozone by cylindrical vessel fed and contact with the acetic acid solution stream that flows downward under about 75 (24 ℃) temperature.Apply enough pressure to keep the low 2.5%(volume of the flammability limit of acetate in oxygen) or aerial 3.8%(volume) (being 8 pounds/square inch (gauge pressures) in air, is 12 pounds/square inch (gauge pressures) in oxygen).
The ozonize time is variable, but finds, and it acts on instantaneous substantially finishing, and on the other hand, excess processes is also harmless.When the treatment time is lower than half an hour, obtain good result, be generally about 1 to 15 minute.Calculate by handled acetate weight, the ozone amount scope of recommendation is about 3ppm to 5000ppm.Except that the problem of cost aspect, the ozone concn height is harmless.
Can in officely why not be dissolved under the existence of known oxide catalyst of acetate about 0.001% to the 5.0%(weight of consumption) carry out the catalysis ozone disaggregating treatment.The catalyzer that is suitable for is metal or the metal oxygen oxide compound that is selected from elements such as manganese, platinum, palladium, silver, rhodium, ruthenium, rare earth (caesium), nickel, chromium, cobalt.If desired, catalyzer and suitable carrier such as diatomite, gac, silicon-dioxide, silicon carbide, aluminum oxide, zeolite (faujusite) can be waited mixing mutually.In fixed-bed reactor, use catalyzer better, and ozone decompose and can carry out with continuous or intermittent mode to the temperature of 125 (52 ℃) at 70 °F (21 ℃).As long as it is not be no more than flammability limit, harsh to the temperature and pressure conditional request.
Reactive oxidants material or complex compound that iodide in the acetate, unsaturated materials and carbonyl impurities obviously can be separated with acetate when needing with ozone reaction formation.With this solution by gac, molecular sieve zeolites (comprising shape-selective zeolite) or H
+Shape ion exchange resin, or from complex compound, distill out pure acetate, can finish this class and separate.Through with activated carbon treatment by acetate carbonylation of methanol acquisition and that cross with ozonize, permanganate time is compared with the acetate with ozonize only, is greatly improved.Introduced the method for removing iodide with the macroreticular strong-acid cation-exchange resin from acetate in the United States Patent (USP) 4615806, this paper draws and is reference.
Can understand the present invention more fully with reference to the following example, embodiment has exemplified at present in order to implement best mode of the present invention.Measure permanganate time by following method among the embodiment:
In in the band scale cylinder that 50 milliliters of acetate are housed, adding 1 milliliter of 0.1N potassium permanganate solution under the room temperature.Cover cylinder and shake, and start timing register immediately and measure the terminal point required time that becomes the succinite look by purple,, express the content of unsaturated materials, iodide and carbonyl impurities this and canonical reference colour contrast.
Embodiment 1:
With acetic acid (the use halogen promoted rhodium catalyst of 185 grams by freezing purifying, low water content makes acetate with methanol carbonylation) mixing makes it to contain the crotonaldehyde of 231ppm and the ethyl crotonaldehyde impurity of 224ppm, and have 0.1 minute permanganate time, and use the ozone of making by air (ozone content is the 0.5%(volume in the air) again) handled 30 minutes.
Embodiment 2:
Handling by the method for embodiment 1 with ozone does not have the acetic acid by freezing purifying that is mingled with, and be 10 minutes and 19 minutes the duration of contact of itself and ozone.
Embodiment 3:
Acetic acid with freezing purifying is doped with ethyl crotonaldehyde (23.2ppm), presses the method for embodiment 1 with ozone and handles.
Embodiment 4:
Compare by the Glacial acetic acid (label is T-840H) that separates the sampling of cat head outflow component and with untreated sample with ozonize.
Embodiment 5:
With ozone by 1 minute with the Glacial acetic acid sample that to handle two labels 3 minutes different duration of contact be V783, and compare with untreated samples.
Embodiment 6:
In 0.5%(weight) in the presence of the manganese dioxide-catalyst, with the untreated Glacial acetic acid that uses among the ozonize embodiment 5, do two different tests, and with do not add catalyzer and compare with the sample of ozonize and with the sample of 0.5% Manganse Dioxide and air handling.
The test-results of embodiment 1 to 6 and the testing data I that is listed in the table below:
Table 1
Table 1(is continuous)
*Mix crotonaldehyde and ethyl crotonaldehyde
*Mix the ethyl crotonaldehyde
Embodiment 7 to 13:
In the following example, by after the ozone disaggregating treatment again through activated carbon treatment, permanganate time is further improved.Even the acetic acid sample that pottle is crossed with ozonize (acetate that uses the promoted rhodium catalyst of halogen to be made by the low water content carbonylation of methanol) is following to the gac in overflow bed system or the trickle bed system in room temperature and environmental stress.The results are shown in down tabulation 2.
Table 2
The embodiment permanganate time (minute)
7. untreated Glacial acetic acid 0.25
8. the acid 1.5 of ozonize
9. ozone and gac
*The acid of handling (overflow bed) 2.5
10. ozone and gac
*The acid of handling (trickle bed) 4.5
11. ozone and gac
*The acid of handling (overflow contactor) 2.0
12. ozone and gac
*The acid of handling (trickle bed)＞10.0
13. gac only
*The Glacial acetic acid of handling 0.25
＊Calgon F300
*Cocoanut charcoal
Claims (12)
1, a kind of purification contains the method for the acetate of halogenide, unsaturated materials and carbonyl impurities, and its improvements are to make described acetate to contact with capacity ozone, and make above-mentioned oxidation of impurities, collect the acetic acid product that has improved permanganate time then.
The process of claim 1 wherein that 2, based on the weight meter of processing acetate, the ozone amount that is contacted is greater than about 3ppm.
3, the method for claim 2, wherein acetate contacts with ozone in the presence of oxide catalyst.
4, the method for claim 3, wherein based on acetate weight meter, the catalyst consumption scope is 0.001% to 5.0%.
5, the method for claim 4, catalyzer wherein are metal or the metal oxides that is selected from manganese, platinum, palladium, silver, rhodium, ruthenium, rare earth, nickel, chromium and cobalt metal element.
6, the process of claim 1 wherein that unsaturated materials and carbonyl impurities, above-mentioned acetic acid product also will contact with gac in order to remove iodide.
7, a kind of method that in the presence of water and halogenide promotor, prepares acetate by the catalytic methanol carbonylation of rhodium, wherein the improvements of halogenide, unsaturated materials and carbonyl impurities in the purifying acetic acid being comprised makes described acid contact with capacity ozone, and make above-mentioned oxidation of impurities, collect acetic acid product then with improved permanganate time value.
8, the method for claim 7, wherein based on handled acetate weight meter, the ozone amount that is contacted is greater than about 3ppm.
9, the method for claim 2, wherein acetate contacts with ozone in the presence of oxide catalyst.
10, the method for claim 9, wherein based on acetate weight meter, the catalyst consumption scope is 0.001% to 5.0%.
11, the method for claim 10, catalyzer wherein are metal or the metal oxides that is selected from manganese, platinum, palladium, silver, rhodium, ruthenium, rare earth, nickel, chromium and cobalt metal element.
12, the method for claim 7, wherein in order to remove iodide, unsaturated materials and carbonyl impurities, above-mentioned acetic acid product also will contact with gac.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13784487A | 1987-12-23 | 1987-12-23 | |
| US137,844 | 1987-12-23 |
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| Publication Number | Publication Date |
|---|---|
| CN1035496A true CN1035496A (en) | 1989-09-13 |
| CN1022238C CN1022238C (en) | 1993-09-29 |
Family
ID=22479283
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88108769A Expired - Lifetime CN1022238C (en) | 1987-12-23 | 1988-12-22 | Purification of acetic acid with ozone |
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|---|---|
| EP (1) | EP0322215B2 (en) |
| JP (1) | JPH01211548A (en) |
| KR (1) | KR0139822B1 (en) |
| CN (1) | CN1022238C (en) |
| AU (1) | AU618567B2 (en) |
| BR (1) | BR8806821A (en) |
| CA (1) | CA1313676C (en) |
| DE (1) | DE3874107T2 (en) |
| ES (1) | ES2034275T5 (en) |
| NO (1) | NO885721L (en) |
| NZ (1) | NZ227447A (en) |
| ZA (1) | ZA889590B (en) |
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| US4895977A (en) * | 1988-12-12 | 1990-01-23 | Pennwalt Corporation | Purification of alkanesulfonic acids using ozone |
| GB9100216D0 (en) * | 1991-01-05 | 1991-02-20 | Bp Chem Int Ltd | Process |
| US5097069A (en) * | 1991-04-08 | 1992-03-17 | Eastman Kodak Company | Process for decomposing α,β-unsaturated carbonyl compounds in refining acetic anhydride and/or acetic acid |
| JP3220234B2 (en) * | 1992-07-07 | 2001-10-22 | ダイセル化学工業株式会社 | Purification of acetic anhydride or a mixture of acetic anhydride and acetic acid with ozone |
| JP3332594B2 (en) | 1994-08-12 | 2002-10-07 | ダイセル化学工業株式会社 | Acetic acid purification method |
| JP4368026B2 (en) * | 2000-02-17 | 2009-11-18 | ダイセル化学工業株式会社 | Purification of crude acetic anhydride and production of polyoxytetramethylene glycol using acetic anhydride |
| JP2002037756A (en) * | 2000-05-18 | 2002-02-06 | Daicel Chem Ind Ltd | Acetic anhydride |
| JP4861563B2 (en) * | 2001-04-24 | 2012-01-25 | 昭和電工株式会社 | Method for purifying lower aliphatic carboxylic acid, method for producing lower aliphatic carboxylic acid by the purification method, and lower aliphatic carboxylic acid obtained by the production method |
| JP5486299B2 (en) * | 2006-04-14 | 2014-05-07 | セラニーズ・インターナショナル・コーポレーション | Method for reducing aldehyde concentration in target stream |
| US7485749B2 (en) | 2006-08-22 | 2009-02-03 | Lyondell Chemical Technology, L.P. | Preparation of acetic acid |
| WO2016135630A1 (en) | 2015-02-25 | 2016-09-01 | Sabic Global Technologies B.V. | Process for removing impurities from acetic acid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1138946A (en) * | 1965-05-07 | 1969-01-01 | Ici Ltd | Process for the decomposition of formic acid |
| JPS5257110A (en) * | 1975-11-06 | 1977-05-11 | Nippon Oil & Fats Co Ltd | Purification process for fatty acids |
| JPS5564545A (en) * | 1978-11-06 | 1980-05-15 | Daicel Chem Ind Ltd | Purification of acetic acid |
| DE3612504A1 (en) * | 1985-09-30 | 1987-04-09 | Hoechst Ag | METHOD FOR SEPARATING IODINE AND ITS COMPOUNDS FROM CARBONYLATING PRODUCTS CONTAINING CARBBONYLATION OF DIMETHYL ETHER, METHYL ACETATE OR METHANOL |
| DE3823645C1 (en) * | 1988-07-13 | 1989-11-30 | Hoechst Ag |
-
1988
- 1988-12-14 CA CA000585855A patent/CA1313676C/en not_active Expired - Lifetime
- 1988-12-21 NZ NZ227447A patent/NZ227447A/en unknown
- 1988-12-21 ES ES88312118T patent/ES2034275T5/en not_active Expired - Lifetime
- 1988-12-21 EP EP88312118A patent/EP0322215B2/en not_active Expired - Lifetime
- 1988-12-21 DE DE3874107T patent/DE3874107T2/en not_active Expired - Lifetime
- 1988-12-22 NO NO88885721A patent/NO885721L/en unknown
- 1988-12-22 AU AU27318/88A patent/AU618567B2/en not_active Expired
- 1988-12-22 ZA ZA889590A patent/ZA889590B/en unknown
- 1988-12-22 CN CN88108769A patent/CN1022238C/en not_active Expired - Lifetime
- 1988-12-22 BR BR888806821A patent/BR8806821A/en not_active IP Right Cessation
- 1988-12-23 KR KR1019880017324A patent/KR0139822B1/en not_active IP Right Cessation
- 1988-12-23 JP JP63323829A patent/JPH01211548A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110072836A (en) * | 2016-12-19 | 2019-07-30 | 沙特基础工业全球技术有限公司 | The method of purification of acetic acid |
| CN109776306A (en) * | 2019-02-26 | 2019-05-21 | 安徽雪郎生物科技股份有限公司 | A kind of preparation method of resin-grade succinic acid |
| CN109776306B (en) * | 2019-02-26 | 2021-12-07 | 安徽雪郎生物科技股份有限公司 | Preparation method of resin-grade succinic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0322215B2 (en) | 1994-11-30 |
| JPH01211548A (en) | 1989-08-24 |
| KR0139822B1 (en) | 1998-07-01 |
| DE3874107D1 (en) | 1992-10-01 |
| KR890009838A (en) | 1989-08-04 |
| ES2034275T5 (en) | 1995-08-16 |
| AU2731888A (en) | 1989-06-29 |
| ZA889590B (en) | 1989-09-27 |
| CN1022238C (en) | 1993-09-29 |
| NO885721L (en) | 1989-06-26 |
| EP0322215B1 (en) | 1992-08-26 |
| BR8806821A (en) | 1989-08-29 |
| DE3874107T2 (en) | 1995-07-13 |
| ES2034275T3 (en) | 1993-04-01 |
| NZ227447A (en) | 1992-01-29 |
| CA1313676C (en) | 1993-02-16 |
| AU618567B2 (en) | 1992-01-02 |
| NO885721D0 (en) | 1988-12-22 |
| EP0322215A1 (en) | 1989-06-28 |
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